Biaxally stress-oriented plastic sheet laminated with nbr adhesive to rubber-coated paper

ABSTRACT

Slippage-resistant, flexible packing blankets for letterpress and printing blankets for offset are made from a high tensile strength, biaxially stress-oriented plastic sheet which is adhesively laminated to a tough, dimensionally stable, high tensile strength, tear-resistant paper, such as Kraft paper, tympan paper or elastomer impregnated paper sheet as an extensible thermosetting adhesive, a phenolic resin-NBR rubber mixture, reacted with a curing agent such as polyisocyanate, is used for laminating. The adhesive is cured at room temperature or at a temperature below that which relaxes the stress-oriented plastic sheet. Superior wear-resistance and high quality of printing have been demonstrated for the blankets of the invention. The blanket is useful as an inking member in letterpress printing of the wraparound press type, and can also be used for the packing material for the impression cylinder in gravure type of printing.

United States Patent 1191 Gurin et al.

[ 1 Apr. 9, 1974 1 1 BIAXALLY STRESS-ORIENTED PLASTIC SHEET LAMINATED WITH NBR ADHESIVE TO RUBBER-COATED PAPER [76] Inventors: Emanuel Gurin, Box 10142,

Caparra Heights, P.R. 00922;

Antonio Vazquez, 193 Nueva St., Vi11a Gawlina, PR. 00917 [22] Filed: Nov. 23, 1971 [21] Appl. No.: 201,544

Related U.S. Application Data [63] Continuation-impart of Ser. No. 842,993, July 18, 1969, abandoned, which is a continuation-in-part of 3,370,104 2/1968 OBricn et al. 260/837 3,652,376 3/1972 Bowdcn 161/159 3,663,353 5/1972 Long et all 161/184 3,504,627 4/1970 Elder et al. 101/395 3,649,439 3/1972 Ross 161/165 3,647,919 3/1972 Lee 260/842 Primary E.\' aminerGeorge F. Lesme's Assistant E.\'aminerWil1iam R. Dixon, Jr.

[5 7] I ABSTRACT slippage-resistant, flexible packing blankets for letterpress and printing blankets for offset are made from a high tensile strength, biaxially stress-oriented plastic sheet which is adhesively laminated to a tough, dimensionally stable, high tensile strength, tear-resistant paper, such as Kraft paper, tympan paper or elastomer impregnated paper sheet as an extensible thermosetting adhesive, a phenolic resin-NBR rubber mixture, reacted with a curing agent such as polyisocyanate, is used for laminating. The adhesive is cured at room temperature or at a temperature below that which relaxes the stress-oriented plastic sheet. Superior wearresistance and high quality of printing have been demonstrated for the blankets of the invention. The blan- [56] References Cited ket is useful as an inking member in letterpress print- UNITED STATES PATENTS ing of the wraparound press type, and can also be used 3,049,442 8/1962 Haines et al. 117/1196 for the packing material for the impression cylinder in 3,147,698 8/1964 ROSS 101/1492 gravure type of printing 2,673,826 3/1954 7 2,402,706 6/1946 Sprigg 101/415.l 5 Claims, 7 Drawing Figures I A-VULCANIZED ELASTOMER WX\Q B-PAPER SHEET C-EXTENSIBLE THERMOSETTING W/N ADHESIVE CYLINDER Y D-BIAXIALLY STRESS-ORIENTED .E-ANCHOR ccnms PLASTIC SHEET DATENTEBAPR 9 1974 3.802.952

C EXTENSI BLE THERMOSETTING ADHESIVE E-ANCHOR COATING D- BIAXIALLY STRESS-ORIENTED PLASTIC SHEET J INVENTORS A EMANUEL GURIN ANTONIO VAZQUEZ BY MW z ATTORNEY BIAXALLY STRESS-ORIENTED PLASTIC SHEET LAMINATED WITH NBR ADHESIVE TO RUBBER-COATED PAPER The present application is a continuation-in-part of our co-pending application Ser. No. 842,993 filed July 18, 1969, now abandoned, which in turn is a continuation-in-part of our application Ser. No. 815,316 filed Apr. 11, 1969, now US. Pat. No. 3,616,178.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention lies in the field of packing blankets and printing blankets used in letterpress printing and printing machines of the offset type. The packing and printing blankets of the invention comprise laminated sheets of wear-resistant construction embodying a vulcanized elastomeric solvent-resistant surface layer of a smooth paper backing laminated to a biaxially stress-oriented, high tensile strength plastic sheet. The paper underlying the vulcanized elastomeric surface layer provides smoothness, compressibility and shock absorbing properties. The blanket withstands severe deformation upon application of printing forces and recovers its shape quickly. If the plastic sheet is re placed by strong cloth, the paper tears away from the clamps and detracts from printing quality by causing wrinkling of the paper printed during normal operation of the press.

2. Description of the Prior Art I Flexible, laminated paper press blankets and packing blankets of the type shown in Fennone U.S. Pat. No. 1,891,150 and in Page US. Pat. No. 2,544,279 have long been known. These blankets employ Kraft or tympan paper sheets in one or more plies which-are laminated together with a starch-based adhesive. The blan- .ket of Fennone includes a heavy and porous paper ply sheets, such as polyvinyl chloride, cellophane or rubber hydrochloride, in printers blankets which are intended to combine a smooth working surface with a resilient backing, as shown in Fredericks US. Pat. No. 2,792,321 and Vasel U.S. Pat. No. 2,285,763. The plastic top sheet of the blanket did not resist embossing and deformation and caused excessive wear of the printing plate in high speed printing.

Conventional woven fabric-reinforced lithographic printing blankets have been tried as packing blankets for letterpress printing but are unsatisfactory because the printing quality is poor, e.g., the dots are blurred, the blanket creeps during printingand tears awar from the grippers, and excessive wrinkling and buckling of the printed paper sheet occurs due to the high elongation and relatively poor dimensional stability of the material as apacking.

Mylar sheet material which is not reinforced at the pin openings laminated to tympan paper has been used commercially, Mylar side up (for protection of paper from the oil which is used on the second printing machines or units). As the top packing material, in thicknesses of 10-40 mils, for letterpress printing, Mylar quality deteriorates very rapidly at the end of the run to add to the expense for high quality printing. I

Elastomer coated tympan paper in total thicknesses up to 12 mils has been used as the top packing sheet in letterpress printing but has been unsatisfactory because it embosses just as quickly, and in certain cases even more quickly, than the Mylar sheet laminated tympan paper packing referred to above, and this embossing further causes poor printing quality. This. packing causes wrinkling of the paper sheet being printed which detracts further from the quality. Accordingly, the thin elastomer-coated tympan paper is less desirable than the Mylar laminated tympan paper in respect to printing quality even though it has better properties in respect to plate wearing.

Elastomer-coated tympan paper in total thickness of greater than 12 mils is unsatisfactory because the packing tears away from the grippers. Once the packing tears, the plate is damaged and the press must be shut down. The pressman is constantly on the alert for this tearing at the clamps.

Reinforcing the edge openings of. elastomer coated tympan paper at the clamps has been tried but it was not judged satisfactory because of the high cost and because no more than 700,000 impressions were achieved before the printing quality failed.

Thus all of the prior art packing blankets for letter press have been deformed and have been found to cause excess damage and wear at the surface of the printing plate. This results in breakdown of the machine. Shut-downs during printing operations are costly and the pressman must be constantly on the alert to a breakdown caused by the tearing of the blanket from the cylinder or by the wearing of the printing surface.

. It was surprising to find that Mylar sheet laminated to paper which is provided with a coating of elastomer on the outer surface thereof produced a IO-fold increase in packing life in letterpress printing with normal handling if reinforced at the clamps or at the pin openings or if an anchor coating is applied in between the Mylar surface of the laminated packing and the surface that is supporting it. If this anchor coating is ab-' sent, or if the pin ends of the blanket are not reinforced, thelife of the laminated Mylar and paper sheet coated with elastomer on the outer surface thereof (before tearing) in letterpress printing is only a few thou sand impressions. Without the edge or pin reinforcement or without the anchor coating on the Mylar sur face, the Mylar laminated paper coated with elastomer on the paper side is thus greatly inferior in its tendency to wear at the clamps than rubber coated tympan paper and than the conventional Mylar-tympan laminates.

SUMMARY OF THE INVENTION The present invention relates to slip-resistant, Mylarreinforced, wear-resistant, elastomer packing blanket and elastomeric printing blanket constructions which are subjected to severe deformation upon the application of printing forces and which recover their original shapes upon removal of these forces as a result of the unique combination of the structure and the materials employed in the manufacture.

The novel printing blanket and packing blanket structures are provided by the laminated reinforcement of a biaxially stress-oriented Mylar (polyethylene terehaving a thickness of between about 3 and about 28 mils, the thickness of the Mylar or acetate sheet reinforcementbeing generally, but not necessarily, limited to being less than the thickness of the coated paper. The Mylar or acetate sheet is adhered to the elastomercoated paper with an extensible thermosetting adhesive and the two-layer composite is coated on the plastic side with an anchor coat ranging from friction to a pressure sensitive adhesive coating. 7 I h Resistance to slipping is provided by reinforcing at the pin openings or by providing an anti-slipcoating between the bottom face of the top blanket and the supporting surface to provide a packing blanket embodiment that resists tearing out of the clamps during regular usage and handling. The slip resistant surface may be produced by texturing the face or may be in the form of an anchor coating comprising frictionimparting ingredients or a pressure sensitive adhesive coating. The stresses created alongthe longitudinal direction of the blanket against the cylinder'during high speed rotation and during starts and stops are alleviated and equalized by the new blanket. The elastomercoated paper cushions the vertical shock stresses imparted by the printing cylinder. The biaxially stressoriented plastic film limits the degree of lateral elongation of the paper sheet and makes the paper more resistant to tearing. The thicknesses of paper and plastic sheet are selected to adapt the blankets for existing printing cylinders in a total single blanket thickness of between 10 and 77 mils and up to 158' mils in multiple blanket assembly. These one and two-piece blankets may be used with or without added packing material.

The extensible thermosetting adhesive has a degree of extensibility of at leastlSO percent, a high rate of elastic recovery and is preferably cured at room te'm-' p'e'rature to provide a'dimensionally stable bond which is resistant to the vertical and lateral shock forces to which the laminated blanket is subjected and which is also resistant to aging solvents and peeling forces,

A'phenolic resin-NBR mixture which sets with curing agent at room temperature or temperatures below those that relax the, biaxially stressed plastic is used as the adhesive. This mixture is reacted with polyisocy'anate of the type shown in Bunge et al., US. Pat. No.

2,855,421 granted Oct. 7, 1958, said polyisocyanate, being obtained byreacting a polyhydric alcohol with an organic diisocyanate in quantities such that more than land not more than l.7'isocyanate groups are present per hydroxy1group, the preferred polyisocyanate being The Mylar-paper laminate which is coated with a vulcanized solvent-resistant elastomer on the peper side provides a surface which is suitable for printing machines of the offset type. This printing blanket may be used as a one-piece blanket with or without conventional unde'rpacking for letterpress or offset printing.

When the blanket as so described is used, it exhibits unusually long wear and provides high quality printing. More than 7,000,000 impressions have been achieved in high speed letterpress printing without any noticeable deformationor embossing of the surface. The high quality of the printing was unchanged and the test was stopped before the printing deteriorated. The upper limit for wearing is not known. It is remarkable that the life of the plate is substantially increased and the cost of high quality printing reduced.

Novel packing and printing blankets and a preferred novel method for their manufacture provide superior quality of printing. The new blankets are long wearing and have been used in high speed letterpress printing for more than 7,000,000 impressions without noticeable deformation or embossing of the top surface which consists of a thin vulcanized rubber coating. The general blanket construction, as shown in the drawing, comprises:

layers A E below, or i layers A D and edge and pin opening reinforcements in the blanket as shown in FIGS. 5-7."

It is an'essential feature of the novel method of the invention that the surface coating of vulcanized elastomer be applied to the paper sheet in the desired thickness and vulcanized at elevated temperature before the paper sheet is bonded to the biaxially stress-oriented plastic sheet with the extensible thermosetting adhesive. Preferably, the adhesive is applied to the back of the paper sheet at room temperature from solvent solution to precisely predetermined thickness within the range shown above. Curing of the adhesive is at room temperature and there is no high temperature condition to which the biaxially stress-oriented plastic sheet is subjected which would relax the plastic and distort it in either the thickness or longitudinal dimension. Accuracy and dimensional stability are'thereby achieved. Then the plastic face is coated with an anchor coat deposited from solution. The solvent is evaporated at temperatures below C. to prevent relaxing of the plastic sheet member.

If desired, a pressure sensitive adhesive coating may be applied to the surface coating of vulcanized elastomer in a thickness from 0.001 to 0.004 inches and this adhesive coated blanket in contact with the metal of the cylinder may be used as the packing in a single blanket or in a multiple blanket packing assembly for letterpress printing. 1

It is an object of the invention to provide a wearresistant blanket for packing or offset printing purposes comprising a biaxially stress-oriented plastic sheet laminated with low temperature curing thermosetting adhesive to a tough, high tensile strength paper sheet, the paper sheet being first sealed with a solvent or ink resistant vulcanized elastomer coating and then laminated to the plastic sheet which is provided with a thin anchor coating.

It is a further object of the invention to provide oneand two-piece assemblies of the aforesaid laminated blanket in which a lower packing blanket of the twopiece assembly is mounted on the printing cylinder with the vulcanized elastomer-coated paper face in contact with the metal of the cylinder and the anchor-coated plastic sheet thereof supporting the anchor-coated plastic surface of the upper blanket.

A further object of the invention is to provide a oneor two-piece assembly of the aforesaid laminated blanket in which a lower packing blanket of the two-piece assembly is mounted on the printing cylinder and secured thereto with a pressure-sensitive adhesive.

A further object is to provide a four-layer blanket, layers A-D above, with edge or pin reinforcement elements at the end of the blanket.

A further object is to provide two-piece packing assemblies for mounting to a printing cylinder in which the aforesaid blanket of the invention is supported by a conventional underpacking, such as paper, latexsaturated paper or a printing blanket.

It is a further object of the invention to provide a novel method for manufacturing a wear-resistant blanket comprising the steps of vulcanizing a solvent or ink resistant coating to a smooth, tough paper sheet and thereafter bonding the paper sheet to a stress-oriented plastic sheet by means of extensible thermosetting adhesive at a temperature whereby the dimensions of the blanket are not distorted.

I It is still a further object of the invention to provide a flexible blanket or blankets in two-piece assemblies ranging in thickness between and 158 mils for fitting the undercut in commercial printing cylinders used in,

letterpress printing and in offset printing and in even higher thickness where more than two blankets are assembled, such as in newspaper printing.

Other and further objects and advantages of the invention will become apparent from the accompanying drawing, the subsequent description and the examples.

BRIEF DESCRIPTION OF THE DRAWING FIG. 1 is a diagrammatic section of a top packing blanket of the invention against a packing cylinder in letter press printing which is the same relationship for the printing cylinder in offset printing and shows the placement of the anti-slipping or anchor-coating of the plastic sheet backing against the metal of the cylinder.

FIG. 2 is a diagrammatic section of an underpacking blanket for a printing cylinder useful in letterpress or in offset printing and shows a pressure-sensitive adhesive coating serving as the anti-slipping coating which is provided over the elastomer-sealed paper surface.

FIG. 3 is a diagrammatic section of a top printing or packing blanket in a two-piece assembly with conventional underpacking with a pressure-sensitive adhesive layer securing the conventional underpacking for letterpress or ofi'set to the metal surface of the cylinder.

FIG. 4 is a diagrammatic section of an underpacking in a two-piece assembly with the pressure-sensitive adhesive coating provided at the surface of the elastomercoated paper, the anchor coat engaging the anchorcoated surface of the top packing blanket of FIG. 1 and the pressure-sensitive adhesive contacting the metal of the cylinder.

FIG. 5 is a fragmentary plan view of the blanket of this invention which is clamped to the cylinder by clamps and/or pins, as shown in Gurin US. Pat. No.

3,045,595, issued July 24, 1962, and shows a heavy tympan paper glued at an edge of the blanket for attachment to the cylinder.

FIG. 6 is a fragmentary cross-sectional view along line 6-6 of FIG. 5 showing the blanket disposed on pins which project from a surface of the cylinder.

FIG. 7 is a fragmentary plan view of a modification of the blanket of this invention showing that grommets or metal inserts can be used for added strength.

The laminated embodiments shown in FIGS. 1-4 are prepared by selecting a biaxially stress-oriented, tough, high tensile strength plastic sheet, such as polyethylene terephthalate or cellulose triacetate, in the required thickness and by laminating this plastic sheet to the paper sheet. The paper B may be Kraft paper, tympan paper, or rubber impregnated paper like the one set out in Hechtman et al. US. Pat. No. 3,026,217, which constitutes a tough compressible paper sheet. This type of paper is also described in the product of Martin US. Pat. No. 3,036,950 and the products of Fiegley et al. US. Pat. Nos. 2,786,759 and 2,905,583. These papers have polymerized natural or synthetic rubber latex added to the beater or to the nip of the loosely bonded fibers prior to rolling during the papermaking process. The amount of rubber or synthetic resin elastomer added is generally between 30 and 120 parts per 100 parts by weight of dry paper fibers. The rubber or resin is selected to give high resistance against tearing and compressibility, as shown in the above-cited Hechtman et a1. patent.

The laminating adhesive is applied in a thickness of between 1 and 4 mils to the back of the paper sheet and a polyisocyanate curing agent permits the adhesive to be cured at room temperature so that there is no high temperature condition to which the plastic sheet is subjected, thereby eliminating distortion and permitting accuracy or dimensioning to within one ten-thousandth of an inch.

' clamping edges and the pin openings to prevent tearing during high speed printing.

As shown in the plan view of FIG. 5, a heavy tympan paper strip 14 is adhesively secured to the rectilinear edge of the blanket. The adhesive bond which adheres the strip 14 to the biaxially stress-oriented plastic sheet D, as shown in' sectional view in FIG. 6, performs an edge-reinforcing function at both ends of the blanket which are mounted onto the cylinder on machinery of the type'shown in Gurin US. Pat. No. 3,045,595, and specifically in FIG. 2 therein.

The tympan paper strip 14 serves to protect the blanket from indentation by the tightening roll which is held in position by the pawl and wheel in the mounting machine of Gurin US. 'Pat. No. 3,045,595. The roll presses against the paper at one end of the blanket and the other end of the blanket is mounted on a pin, as shown in FIG. 2 of the Gurin patent. The pin end of the blanket is pierced with a hole which fits over the pin 15, as shown in FIGS. 5 and 6 herein. The heavy reinforcing paper strip is also piercedJWhen the bolt of the cylinder (not shown) is tightened on the pin 15, the lower edge of the bolt presses against the heavy reinforcing strip 14.

Grommets16, surrounding the openings through the reinforcing strip and blanket, as shown in FIG. 7, provide additional reinforcement.

Thus, the present blanket with layers A-D and edge reinforcing strip is useful with conventional mounting machineryThe strip may be of material other than paper, e.g., plastic such as nylon, aluminum, steel, leather, cloth, woven fiberglass fabric and the like, and in appropriate thickness, an excellent reinforcing result can be achieved. Stiff, high tensile strength plastic material, such as polycarbonate resins, known under the Trademark DELRIN, and polyphenylene oxide resin, may also be used with good results.

The blanket without reinforcing clamps, pins and metal inserts at the openings does not provide long life in letterpress printing as a packing blanket or in offset printing and does not provide good print quality.

Plant runs were made for high speed printing using metal plates and the blanket having layers A-D without the present reinforcement as a packing blanket. Theblanket pulled away from the clamps and the print quality became very poor after 4,000 impressions. After this unsatisfactory run and because of the rapid deterioration of printing quality which resulted at the end of the run, there appeared to be no possibility of utilizing the four-layer blanket, e.g. IayersA-D, in any practical manner for commercial printing. Surprisingly, when the reinforcing means were provided in accordance with FIGS. 5-7 herein, the printing operation on the same press produced 4,000,000 impressions and superior printing quality was maintained throughout the run. This is to be compared with more than 7,000,000 impressions which were achieved. with the blanket having layers A-E. As in that case, more printing could have been carried out since there was little wear, but 'the production schedule did not permit it.

It was totally unexpected to find that the blanket without the anchor coating E could be reinforced at the ends and provide long printing life and excellent printing quality.

The, anchor coating E is preferably a thermosetting anti-slipping coating which consists of a thermosetting adhesive of the type used for'laminating, or it may be a pressure-sensitive adhesive. The pressure-sensitive adhesive is..coated from solvent dispersion wherein the solventis a volatile, normally liquid organic solvent which does not attack the plastic sheet and the adhesive may. contain dissolved polymer components, such as vinyl ester polymer (Vinylite 'AYAF), chlorinated vinyl chloride polymer, isobutylene polymer, SBR rubber, chlorinated rubber, natural rubber,- butyl rubber, polyurethane, ru'bber'and the like, and a tackifier suchas wood, rosin, glycol esters of rosin or maleic anhy dride modified ester gum and the like. Other agents, such as softening agents, stabilizers, liquid plasticizers, etc., may be present. The tackifiers are well-known commercial products sold under such names as Wood Rosin WG, Polypale Ester No. 2, Kenflex A,Cumar V /2, Staybelite", Piccolyte, Polypale Ester No. 10, and Vistac-l (A low molecular weight hydrocarbon polymer produced by Advance Solvents and Chemical Corporation (New York, N.Y.) Saybolt viscosity (Univ.) (210F.) 2,800 +sec., density 7.5 lbs./gal.).

It is also desirable to add one or more stabilizers such as organophosphates, dibasic lead phosphite, phenyl glycidyl ether, dibutyl tin maleate, diglycidyl ether of his phenol, lead salts of organic or inorganic acids, barium and cadmium salts of naphthenic or ricinoleic acids, and one or more antioxidants such as hydroquinone, lecithin, propyl gallate, thiodipropionates including lauryl thiodipropr'ionate, nordihydroguaiaretic acid, butylated hydroxy anisole, diphenyl amine, alpha phenyl naphthylamine, beta phenyl naphthylamine, etc.

The aforesaid adhesive composition, in the practice of this invention, can be spread upon the paper or the plastic film by means of an applicator, following which the applicator can be withdrawn from the adhesive coating without the development of stringiness. For best results, the adhesive coating is spread on the backing to a dry coating thickness of 0.00linch to 0.003inch.

In the selection of an anchor coating E which contains anti-slipping filling components, these components are high oil absorptive thixotropic pigments which stiffen the fluid resinous coating. These high oilabsorptive thixotropic fillers are finely divided, inorganic solids such as short fiber asbestos of 'fine, standard plastic filler grade, pulverized dehydrated silica gel in uncompressed state, e. g. Cab-o-sil, Godfrey L. Cabot Co., PD-244 Silica, Davison Chemical Co., or Santocel, Monsanto Chemical Co., certain natural and/or treated clays which include combined water in their structure (so-called hydrous clays), e.g. bentonite, etc.

The asbestos shorts, silica gel and hydrous clays are employed in small amounts, usually between about 0.5 percent and 5 percent by weight. Each of the three classes of materials is of hydrous nature, having small amounts of water'combined chemically into its makeup, and it is believed that it isthe hydrous quality of each and the great surface area presented that aids in developing the desired rheological properties. The silica gels represented by Cab-o-sil, Santocel and PD-244 Silica are dry rr'e-fliswifigiawaery products'which still contain small amounts of combined water in their gel structure and are submicroscopic particles having an SiO2. content (dry basis) of 99.0-99,7 percent, a free moisture content of 0.2-2.0 percent at I05C. and a negligible content of calcium oxide, magnesium oxide and ferric oxide. ()paline hydrous siliceous minerals, such as hyalite and diatomite, are natural'products comparable to the above manufactured products which in comminuted form can also be used. a

Finely divided solid materials of a hard abrasive nature may be added to impart reinforcement and slip resistance. Thus, pulverized sand, pumice, aluminum carbides, aluminum silicides, garnet, glass, porcelain, blast-furnace slag, etc., represent comminuted abrasive materials which can be used.

DESCRIPTION OF THE PREFERRED EMBODIMENT General Procedure for Assembling and Laminating and Selection of Materials A. Surface Coating of Vulcanized Elastomer Applied to Paper Sheet B The vulcanized elastomer A of the top layer is deposited from an inert volatile solvent solution onto the smooth, dimensionally stable, tough paper B. Kraft paper having a hard surface finish and a Mullen bursting strength of 50 to 200 pounds is provided with a vulcanized synthetic elastomer or vulcanized natural rubber coating in a thickness of from 0.001 to 0.025

good compression set, high cure rate, good tear resistance and abrasion resistance. The vulcanized coatings employ the vulcanizing agent (accelerators and promoters), reinforcing pigments and softeners recommended by the supplier of the material, and have produced Shore A Durometer hardness values lying between 30 and 95. The selection of the elastomermaterial takes into account the compatability with the anchor coating and pressure-sensitive adhesive materials 0 employed and the composition of the printing inks and ink solvents used in thinning the inks or the solvents used for cleaning or wiping.

The thickness of vulcanized elastomer layer A lies between 0.003 and 0.015 inches when the blanket is inches. Thicknesses above 0.025 inches are not neces used for Offset Priming hard Surfaces Such as metal, sary to achieve the desired results and in thicknesses f hes between 0013 and 0-022 Inches when Prmtmg below 0.00linch, it is impossible to achieve the solvent 15 to be done 50ft Surfaces Such as cafdboar In and abrasion protection required for this invention. Set Prmtmg of letter g stock, layer A y be The high strength Kraft paper is commercially avail- (1005 a 0020 Inches, the heavier thlckness able at thicknesses of from 0.00810 0.25 inches. Other glvmg longer strong fiber papers may be used in the same dimen- The top layer of the blanket which is placed next to sions, such as tympan paper, paper made from jute fithe paper in the letterpress machine or which is used as bers, paper made from sisal fibers, and paper made by the printing surface in the offset printing machine is a the sulfite process, but these must be as strong as the cross-linked or vulcanized elastomer compounded in a Kraft paper. hardness range of from -96 Shore A Durometer The elastomer A is dissolved or dispersed in a volatile value, typical vulcanized elastomers being based on solvent with curing agent or accelerator, activator such natural rubber, polyisoprene, NBR rubber, butyl rubas zinc oxide, plasticizer such as stearic acid, softener ber, chlorinated polyisoprene, polyethylene rubber, such as tricresyl phosphate, paraffin, dibutyl phthalate 30 EPDM rubber, polysulfide rubber, silicone rubber, fluand the like, anti-oxidant such as phenyl-ozorosilicone rubber, polyvinyl chloride rubber, ethyl acnaphthylamine or the like, and filler and reinforcing rylate rubber, neoprene rubber, EPR copolymer rubpigment such as carbon black, whiting, clay and the ber, polyurethane rubber of the Elastothane type, like. The mixture is milled, coated onto the paper and fluoro elastomers of the Viton A and Viton B types, vulcanized at 250-340F. for from 15 minutes to sevepichlorohydrin rubbers of the Hydrin type, propylene eral hours. The lower vulcanizing temperatures are preoxide rubbers of the Dynagen type, chlorosulfonate ferred since higher temperatures tenderize the paper. polyethylene rubbers of the Nypalon type and SBR rub- The elastomers in accordance with the table below bers. have been formulated to provide solvent resistance, B. Summary of Elastomer Properties if TAEQ'E Other Out- Abrasion" Solvents Solvents Not standing Resist- Resisted by Resisted by Physical Elastomcr ance Elastomer Elastomer Properties Natural l Alcohols Hydrocarbons High tear rubber resistance Synthetic l Alcohols Hydrocarbons High tear polyisoprenc resistance SBR rubber l Alcohols Aromatic Easy processhydrocarbons ing, low cost Neoprene 3 Aliphatic Aromatic Resists Crys r bb r hydrocarbons hydrocarbons tillization and alcohols and flexing NBR rubber 4 Aromatic and Alcohols Easy processaliphatic ing, low cost hydrocarbons Polyurethane l Aromatic and Alcohols Aging and rubber aliphatic oxidation (ELASTOTHANEW hydrocarbons resistance Polyethyl- 3 Aromatic and Alcohols Resists ozone, acrylatc aliphatic heat and aging rubber hydrocarbons (THlACRlLl Butyl rubber. 3 Alcohols Aromatic and Resists oxidaaliphatic tion and heat hydrocarbons Ethylene 3 Alcohols Aromatic and Resists aging propylene aliphatic terpolymer hydrocarbons Epichloro- 3 Aromatic and Alcohols Resists oxygen hydrin rubber aliphatic and aging (HYDRlN) hydrocarbons Chlorosul- 3 Aromatic and Alcohols Resists heat fonated poly aliphatic ethylene hydrocarbons 11 12 TABLE-Continued Other Out- Abrasinn" Solvents Solvents Not standing Resist- Resistcd hy Resisted hy Physical Elustomcr ancc Elastomcr Elastnmcr Properties (HYPALON)"' Propylene v 3 Aromatic and Alcohols Resists ozone, oxide aliphatic heat and aging (DYNAGEN hydrocarbons Polyl'luoro- 2 Aromatic Chlorinated Resists heat and ethylene and aliphathydrocarbons aging (VlTON ic hydrocarbons and alcohols Polysulfide 4 All None High oxidation (THlOKOL)"" solvents resistance Silicone 4 Aliphatic Aromatic Resists high (polysiloxanc) hyd rohydrocarbons heat carbons Polybutadienc l Alcohols Hydrocarbons Good heat aging Fluorosilicone 4 All None Outstanding solvents chemical resistance Styrcne-iso- 2 Alcohols Hydrocarbons Good oxidation prime-styrene resistance block polymer "Scale of l for high abrasion resistance. 2 for medium in high abrasion resistance. 3 for medium to fair abrasion resistance and 4 for low abrasion resistance. Trademark ofl'hiokol Chemical Corporation Trademark of 'l'hiokol Chemical Corporation "Trademark of B. F. Csoodrich Company Trademark of DuPont "Tradcmark of Generzil Tire and Rubber Company ""lrademark of DuPont 'l'radcmark of'l'hiokul Chemical Corporation C. Blanket Layer Dimensions TABLE Layer of Blanket (ln inches) Undercut of Cylinder (Inches) A B C D E F .0105 .0025 .0030 .0015 .0005 .0010 .0020 .0240 I .0025 .01 H) .0015 .0060 .0010 .0020 .0355 .0040 .0210 .0015 .0080 .0010 .0420 .0025 .0230 .00l5 .0120 .0010 .0020

The friction coating F is applied to the Mylar or cel- Formula 2 Parts lulose triacetate surface. The preferred plastic vehicle 45 Ingredient 4 By weight for the friction coating the aliphatic copolyester con- 5 R rubber 3 parts butadiene 100,0 taining hydrated silica filler and cured with polyisocyag n: i an styrene) 0 inc 0x1 e nate. The thickness of the friction coating may vary Lecithin from 1 to 4 mils and is preferably about 2 mils. The y? H v i y esters O l'OSln same curing cycle as for the laminating adhesive 18 fol- Bakelite Resin BR 14634 1 i0 lowed. This extends the life of the blanket from 10 to v (thermoplastic phenol 20 times that of any comparable blanket of the prior art fmmaldehyde mm) and it is believed that the increased life is due to the Formula 3 curing cycle at room temperature. I P t D F t, d P S .t. Adh Ingredient by Weight refssure' We eslve SI 3R rubber,(3 parts butadiene i000 The following formulae illustrate the anchor coating wi y g y Mwney lSCOSlly based on pressure-sensitive adhesive F. Glycol ester gum 750 Zinc oxide 80.0 Formula I I f Part5 Dlethyl thiurarn dlsulfide 0.3 ingredient 3 weight Zinc butyl dithiocarbamate 0.3 SBR'rubber (3 parts butadiene l2.0 with 1 part styrene) Formula 4 Rosin (specific gravity L08. I Parts melting point l00-150C.) 100 lngrcdient By Weight Graphite (black lead) 6.0 Vmyhte (AYAF fi) 50 Lanolin 2.0 (p lymerized vinyl acetate, Agerite resin antioxidant 0.5 vinyl alcohfil-acetalel ld l-ah h l i Arofene 700 phenolic resin) 36.0

Benzene 29 5 Butyl phthalyl butylglycollate 18 .0

Formula Formula 6 Formula 7 Formula 8 Formula 9 Formula 10 Formula 11 Formula 12 Formula 13 -Continued Ingredient Parlon 1259 Type (white, odorless. non-flammable granular powder, a chlorinated natural rubber) Staybelite Ester 10 (pale, hard resin, glycerol ester of hydrogenated rosin) Dibutyl phthalate Acetone Hexane solvent Ingredient Milled pale crepe Polymerized B-pinene resin Polymerized trimethyl dihydroquinolinc Petroleum oil Ingredient Smoke sheet rubber (milled) Zinc oxide Dehydrogenated rosin Sym-di-B-naphthyl-p-phenylene Lanolin Ingredient Butadiene: 30 styrene copolymer (Mooney Viscosity 50) Milled smoke sheet rubber (natural rubber) Ester of hydrogenated rosin Polymerized trimethyl dihydroquinoline Petroleum oil Ingredient Polyvinyl ethyl ether (intrinsic vis. =2.37) Hydrogenated rosin Phenyl-a-naphthylamine Polyethylene glycol 400 diricinoleate Ingredient Polyisobutylene (high polymer) weight solid polymer) Polyisobutylene (viscous liquid) Ingredient Vistanex MML-IOO (polyisobutylene rubber) Amberol ST-I37K (oil-soluble phenol formaldehyde polymer in solid form) Pentalyn K (Pentaerythritol ester of rosin) Paraftinic process oil (make up to solids in naphtha) Ingredient Polyester-polyurethane rubber Zinc oxide Rosin (specific gravity 1.08, melting point lO0l50C.)

Santolite MPH (condensate product of formaldehyde with aromatic sulfonamide) Graphite (black lead) -Continued Formula 14' Parts Parts By Weight Ingredient By Weight 5.0 Hydrin (polyester rubber) 100.0 5 Agerite resin (aldoI-a-naphthyl 1.0

amine) 10.0 Zinc oxide 50.0 Acetone 60.0 Lanolin 2.0 10.0 Formula 15 52.5 Parts 22.5 1 Ingredient By Weight Pans '7 Ethyl acrylate polymer in acetone 27.5 B w Polyvinyl-acetate-ethyl acrylate 2.4 g 6 Sucrose acetate isobutyrate 5.6 Polymolecular product of ot-methyl 1.9 75.0 S

yrenc l0 Toluene L8 I5 Xylenc 19.9 Formula 16 Parts Ingredient By Weight Y Welsh! Chlorosulfonated polyethylene 12.0 Polychlorinated polyphenyl 12.0 Ethylene glycol ester of polymerized 18.0 2O rosin I Toluene 58.0 Formula 17 Parts Pans Ingredient By Weight y Weight Pale crepe 100.0 Aluminum hydrate 60.0 Polyterpene resin (melting point 30.0 50.0 I 0 Polyterpene resin(melting point 30.0 50.0 115C.)

2.0 Lanolin 10.0 Agerite antioxidant 1.0 Formula 18 Parts Parts Ingredient By Weight By Weight Pure gum reclaim rubber 120.0

100.0 (83.3% rubber hydrocarbon) Zinc oxide 70.0 50.0 Polyterpene resin (melting point 80.0

0.35 70C.) 1 1.50 Liquid hydrocarbon plasticizer 20.0

(heavy, clear liquid composed of high molecular weight hydrocarbons) Parts Agerite antioxidant 2.0 By Weight Formula 19 100.00 Parts Ingredient By Weight 70.0 40 75 Butadiene: 25 styrene (Mooney 50.0

viscosity 70) Parts Polyisobutylene (molecular weight 50.0 By Weight of 100.000

100.0 Glycerol ester of hydrogenated 55.0

rosin (melting point 84C.) Polyisobutylene (molecular weight 5.0

45 of I100) Formula 20 45.0 Parts Ingredient By Weight 5() 0 Polyvinyl ethyl-ether-amorphous 100.0

(intrinsic vis. =2.37) Hydrogenated rosin (melting point 5.0 Parts I 76C) y weight Agerite antioxidant 0.4

Illustrative Example for Paper Layer A 50.0 This example illustrates the manufacture employing 50.0 three species of paper for layers B and Buna-N for layer A. The three species of paper are: (1) high tensile strength Kraft paper with Mullen bursting strength of 90 pounds, (2) tympan paper in thickness of 0.005 inch; and (3) latex impregnated paper in thickness of Pans 0.01 1 inch. A mixture of 100 parts by weight of Buna- By Weight N, 1 part of Santocure1 accelerator (N-cyclohexyl-Z- 288 benzothiazyl-sulfonamide), 1 part of Neozone-A 10.0 (phenyl-a-naphthalamine), 50 parts of carbon black, 4 5 10 parts of dibutyl phthalate, 5 parts of zinc oxide, 2 parts of sulfur and 1 part of stearic acid were milled and 7 0 v dispersed in toluene, there being 1 part of toluene for each part of solids. The mixture was milled and coated nolic ingredients, these being obtained commercially in' the form of solvent solutions, in proportions of about 100 parts of NBR to 75-200 parts of phenolic resin. The preferred form of proprietary chemical is known as Hycar 1041 which is available from the B. F. Goodrich Company as a dispersion in toluene, although it may be obtained from other suppliers such as Firestone Rubber Company under the trade name of Butaprene; Goodyear under the trade name of Chemigum; or American Polymer Company under the trade name Butacryl. The preferred commercial phenolic resin is obtained under the trade name Durez 12687 from the Durez Plastics Division of Hooker Electrochemical Company, North Tonawanda, N.Y. This resin is specifically formulated by the supplier for Buna-N rubber (see The Condensed Chemical Dictionary, 5th Edition, Reinhold Publishing Company, 1956, page 418) and is a fusible and, soluble condensation product of a phenol and formaldehyde having reactive nuclei and methylene bridges between phenolic rings in chain-like molecules of high molecular weight. This phenolic resin is compatible with the NBR. I

The phenol in -.Durez 12687 is preferably an alkyl substituted phenol which is selected-to provide good compatibility with NBR, e.g., p-tertiary butyl phenol, p-amyl phenol, etc. The nitrile content of the l-lycar is in the low to medium range which provides excellent flexibility, eg 2 l-40 percent acrylonitrile content, the

remainder being butadiene.

When higher proportions of phenolic resin are used, 200 .parts of phenolic resin for 100 parts of NBR, thinner adhesive coatings are employed and a vulcanizing agent is added to the solvent solution (toluene) for assisting the cure. NBR vulcanizers are well known and a preferred vulcanizer is benzothiazyl sulfide in an amount of about 2-4 parts of vulcanizer for 100 parts of NBR.'A lso 2 parts of sulfur, 5 parts of zinc oxide, and 2-4 parts of magnesium oxide are added to aid in curing the NBR in.t he adhesive at temperatures of 250350F. for l0 minutes to an hour. Up to parts of paraplex G (Rohm and Haas) polyester plasticizer may be added for enhancing flexibility.

lt-is preferred to use from 80-100 parts of phenolic resin with each 100 parts of NBR rubber formaximum flexibility and all of the ingredients in above'mentioned proportions, e.g., plasticizer, vulcanizer, are added to the toluene system.

The above toluene solution was reacted with an equal weight of 'the polyisocyanate of Example 1 of Bunge et al. U.S. Pat. No. 2,855,421 which was added to the above solvent. The polyisocyanate of Example "1 of Bunge et al is obtained by reacting toluylene diisocyanate with a mixture of trimethylol propane and 1,3- butylene glycol in quantities such that not more than 1.7 isocyanate groups are present per hydroxyl group; 7

This solvent solution of adhesive. components was coated from toluene solvent onto the bottom side of paper layer B in a thicknessof .0015 inches after the solvent was evaporated therefrom at a temperature less than [50F The adhesive coated surface of the paper but was laminated to a biaxially stress-oriented Mylar which had a thickness of .006 inches after which it was cured at 300F. for at least 15 minutes. The laminated product was then coated on the Mylar surface with a friction coating comprising 3 parts by weight of hydrated silica per 100 parts of dry adhesive solids in the same toluene solution as was used for the adhesive layer C. The solvent was evaporated at 100C. This provides the friction coating layer E.

Both printing and packing blankets were prepared in accordance with the dimensions shown in the table under (c) above, Blanket Layer Dimensions.

As mentioned in the Summary of the Invention and as illustrated in the figures of the drawing, the novel packing blankets of the invention provide superior wear-resistance and high quality of printing when used as a packing blanket for letter press printing or as an offset member. The blanket is also generally useful as an inking member in printing. In letterpress printing of the wrap-around press type the present blanket is especially adapted for use as the inking member. In gravure printing, the present blanket may be used as the packing member for the impression cylinder. Accordingly, the term blanket herein is seen to cover the printing application of the present novel blanket in letterpress printing and in gravure printing and also includes the application of the blanket as an inking member for letterpress printing of the wrap-around type.

What is claimed is:

1. An elastomeric flexible laminated blanket adapted for use as a top packing material for letterpress printing or for offset printing comprising:

a tough smooth dimensionally stable high tensile strength, tear-resistant paper selected from the group consisting of Kraft paper, tympan paper and latex-impregnated paper;

said paper being coated with a solvent-resistant vulcanized elastomer having a Shore A Durometer hardness value between about 30 and about said paper being adhexively laminated to a biaxially stress-oriented plastic sheet selected from the group consisting of polyethylene terephthalate and cellulose acetate;

the adhesive of said laminate being a fusible phenolic resin-NBR mixture at 75-2()0 parts resin to parts NBR which is set with a blocked polyisocya' nate obtained by reacting a lower trihydric alcohol with an organic diisocyanate'in quantities such that more than 1 and not more than 1.7 isocyanate groups are present per hydroxyl group curing agent i at room temperature, said adhesive being a thermosetting extensible elastic material having rapid recovery and being cured at a temperature below the relaxation temperature of the plastic sheet; and, i

an anti-slip, solvent-resistant anchor coating for the outside of said blanket, said anchor coating being selected from the group consisting of a nonblocking friction coating and a pressure-sensitive adhesive coating which prevents creeping of said blanket during printing.

2. An elastomeric flexible laminated blanket as claimed in claim 1 for use, vulcanized elastomer side up, as a top packing blanket-for letterpress, wherein said anchor coating is applied to the outer surface of said plastic sheet which is on the bottom of the blanket.

3. An elastomeric flexible laminated blanket as claimed in claim 1 for use, plastic side up, as a top packing blanket for letterpress, wherein said anchor coating is applied to the outer surface of said vulcanized elastomer coated paper which is adapted to be pressed against the cylinder.

4. An elastomeric flexible laminated blanket as claimed in claim 1 for use, vulcanized .elastomer side up, as an offset printing blanket, wherein said vulcanized elastomer layer is between 0.003 and 0.025

inches in thickness, said paper is between 0.003 and 0.028 inches in thickness, and said plastic sheet has a thickness of 0.0005 to 0.016 inches and is provided on its outerside with said anti-slipping coating.

5. A two-piece blanket assembly comprising an underpacking and a top laminated flexible blanket consisting essentially of:

a tough smooth dimensionally stable high tensile strength, tear-resistant paper selected from the group consisting of Kraft paper, tympan paper and latex-impregnated paper;

said paper being coated with a solvent-resistant vulcanized elastomer having a Shore A Durometer hardness value betwen about 30 and about 95;

said paper being adhesively laminated to a biaxially stress-oriented plastic sheet selected from the group consisting of polyethylene terephthalate and cellulose acetate;

the adhesive of said laminate being a fusible phenolic resin-NBR mixture at -200 parts resin to parts NBR which is set with a blocked polyisocyanate obtained by reacting a lower trihydric alcohol with'an organic diisocyanate in quantities such that more than 1 and not more than 1.7 isocyanate groups are present per hydroxyl group curing agent at room temperature, said adhesive being a thermosetting extensible elastic material having rapid recovery and being cured at a temperature below the relaxation temperature of the plastic sheet; and,

an anti-slip solvent-resistant anchor coating for the outside of said blanket on the plastic side, said anchor coating being selected from the group consisting of a non-blocking friction coating and a pressure-sensitive adhesive coating which prevent creeping of said blanket during printing. 

2. An elastomeric flexible laminated blanket as claimed in claim 1 for use, vulcanized elastomer side up, as a top packing blanket for letterpress, wherein said anchor coating is applied to the outer surface of said plastic sheet which is on the bottom of the blanket.
 3. An elastomeric flexible laminated blanket as claimed in claim 1 for use, plastic side up, as a top packing blanket for letterpress, wherein sAid anchor coating is applied to the outer surface of said vulcanized elastomer coated paper which is adapted to be pressed against the cylinder.
 4. An elastomeric flexible laminated blanket as claimed in claim 1 for use, vulcanized elastomer side up, as an offset printing blanket, wherein said vulcanized elastomer layer is between 0.003 and 0.025 inches in thickness, said paper is between 0.003 and 0.028 inches in thickness, and said plastic sheet has a thickness of 0.0005 to 0.016 inches and is provided on its outerside with said anti-slipping coating.
 5. A two-piece blanket assembly comprising an underpacking and a top laminated flexible blanket consisting essentially of: a tough smooth dimensionally stable high tensile strength, tear-resistant paper selected from the group consisting of Kraft paper, tympan paper and latex-impregnated paper; said paper being coated with a solvent-resistant vulcanized elastomer having a Shore A Durometer hardness value betwen about 30 and about 95; said paper being adhesively laminated to a biaxially stress-oriented plastic sheet selected from the group consisting of polyethylene terephthalate and cellulose acetate; the adhesive of said laminate being a fusible phenolic resin-NBR mixture at 75-200 parts resin to 100 parts NBR which is set with a blocked polyisocyanate obtained by reacting a lower trihydric alcohol with an organic diisocyanate in quantities such that more than 1 and not more than 1.7 isocyanate groups are present per hydroxyl group curing agent at room temperature, said adhesive being a thermosetting extensible elastic material having rapid recovery and being cured at a temperature below the relaxation temperature of the plastic sheet; and, an anti-slip solvent-resistant anchor coating for the outside of said blanket on the plastic side, said anchor coating being selected from the group consisting of a non-blocking friction coating and a pressure-sensitive adhesive coating which prevent creeping of said blanket during printing. 